By Glenn Dryhurst (Auth.)
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Extra info for Biological Electrochemistry
The overall picture of the process shown in Fig. 18 was complicated by a report by Parker , who found that under cyclic voltammetric conditions up to five different electrode processes may be observed for the p-benzohydroquinone-p-benzoquinone system in acetonitrile at a platinum electrode. The nature of the reduction processes was found to be highly dependent on electrode history. 5 V vs. , identical to that shown in Fig. 34 V vs. SCE and a new oxidation peak on the next cycle (peak ll a) at E p = - 0 .
Because of the disagreements between the results of Parker  and those of Eggins and Chambers [66,69], a further, more detailed investigation of the electrochemistry of various quinone-hydroquinone systems in nonaqueous solvents was carried out by Eggins and Chambers . A typical slow-sweep cyclic voltammogram for p-benzohydroquinone in acetonitrile is shown in Fig. 24. , exactly the same as proposed by Parker  (see equation for peak l a in Fig. 21). 0 ^ — 1 T. 0 Potential (Vvs. SCE) Fig.
Consideration of the cyclic voltammogram shown in Fig. 38 reveals that reduction peak l l c is somewhat smaller than peak l c . Cauquis and Marbach  also noted that reproducible cyclic voltammograms 1 could not be obtained at sweep rates below 67 mV s~ . In particular, reduction peak ll c could not be observed below the latter sweep rate. These observations have been rationalized by the influence of residual water in the solvent. Thus, it was proposed  that the primary peak l c product, a radical anion (Q~), undergoes partial protonation by this residual water to give a neutral radical (QH-).